3-Hydroxymethacrylic acid methyl ester dimethyl thionosphosphate

ABSTRACT

The compound of the formula   its manufacture and use in pest control.

United States Patent [191 Beriger et al.

[45] Dec.2,l97 5 3-I-IYDROXYMETHACRYLIC ACID METHYL ESTER DIMETHYLTHIONOSPHOSPHATE [75] Inventors: Ernest Beriger, Neuallschwil;

Ladislaus Pinter, Basel. both of Switzerland [73] Assignee: Ciba-GeigyAG, Basel, Switzerland [22] Filed: Apr. 5, 1973 [21] Appl. No.: 348,426

Related US. Application Data [63] Continuation of Ser. No. 136,193 April2|, l97l,

[56] References Cited UNITED STATES PATENTS 3,594.454 7/l9 7l Beriger ctal. 260/941 OTHER PUBLICATIONS Stothers et al., Canadian Journal ofChemistry, Vol. 39 (1961), pp. I389 to 1392.

Primary Examiner-Richard L. Raymond Attorney, Agent, or FirmFrederick H.Rabin; Karl F. Jorda [57] ABSTRACT The compound "of the formula itsmanufacture and use in pest control.

1 Claim, No Drawings 3-HYDROXYMETHACRYLIC ACID METHYL ESTER DIMETHYLTHIONOSPHOSPHATE This is a continuation of application Ser. No. 136,193,filed on Apr. 21, 1971, now abandoned.

This invention relates to pest control agents.

The present invention relates to the compound of formula and itsmanufacture and use in pest control.

The compound according to the invention of formula I is manufactured inknown fashion by reacting dimethylthiochlorophosphate with the methylester of a ahydroxymethylenepropionic acid, or preferably with a saltthereof, e.g. an alkali salt.

The reaction is carried out in an inert, preferably polar solvent suchas dioxane, acetonitrile, dimethylsulfoxide, dimethylformamide, or forexample benzene, toluene, xylene, chlorobenzene and others, attemperatures of 15 to 80C, especially 30 to 70C.

The compounds of fonnula I have a broad biocidal activity spectrum andcan be used for combating various animal and vegetable pests.

They are suitable in particular for combating insect types of storedproduct and grain pests, since they fulfil all the necessaryrequirements of an insecticide for stored products, these being 1. lowlethal minimum concentration for insects 2. low toxicity towards humansand domestic animals 3. an uniform action over many months 4. no residueproblems 5. a faint characteristic smell.

Compared to the similarly consituted compounds of French Pat. No.1530955, or the commercial product PHOSDRIN (Registered Trade Mark) ofthe formula warm blooded toxicity LD 3-7 mg/kg body weight orally (Rats)or DDVP (dimethyldichlorvinylphosphate): warm blooded toxicity LD 50mg/kg body weight orally (Rats), the material of formula I only has alow toxicity of LD 500 mg/kg orally (Rats), but also has the advantagesof stronger insecticidal action, very 'long effective life (more than 4months), increased vapour pressure, lack of residue problems, and afaint characteristic smell. Furthermore it diffuses easily into the gapsbetween stored foodstuffs.

By virtue of these properties the following typical storage pests andcrop pests can be combated with the active substance of formula I:

Oryzaeplzilus su rinamensis Trogoderma gra narium Lasioderma serricorneClrrypmlesles ferrugineu: Stegabium puniceum Necrobia rufipes Simphilusgrana rium Sirophilus aryzue Simpliilns Zen muix -continued Latin NameCommon Name lesser grain borer dried bean beetle Angoumois grain mothRhizoperlhu dominica Acanlhoscelides obtecrus Sitotroga cerealellaNemapagon granellus corn moth Tyrophagus putrescenliae copra mite Acarus.siro flour mite Ephestia kuclmiella Araecerus fasciculams Carpophilushemiplerus Tenebrio malitor Tribolium caslaneum Tribalium destruclorTribolium confusum BIaneI/a germanica Periplanela americana BlallaOrientalis The active substance of formula I can be used as pureconcentrate or in admixture or conjunction with suitable carriers and/oradjuvants.

Suitable carriers and adjuvants can be solid or liquid and correspond tothe substances conventionally used in formulation, technique, forexample natural or regenerated mineral substances, solvents,dispersants, wetting agents, adhesives, thickeners, binders orfertilisers.

The active substance of formula I can be used in pure form, for exampleby treating warmed containers with the agent and allowing the contentsto evaporate.

The active substance can also be formulated in customary solid or liquidfashion and can be used as an emulsion concentrate, spraying powder,,dusting powder, granulate or spray. Of primary use are gas phase,fumigation or sprayed applications. In this way crops such as wheat,rye, barley, oats, millet, rice, maize and other dried fruits can betreated during filling into silo storage, for example on a conveyorbelt, with a liquid formulation of the material of formula I.

Sprayable solutions suitable for direct application contain e.g. mineraloil fractions of high to medium boiling range, particularly over C, suchas diesel oil or kerosene and furthermore coal tar oil or vegetable oranimal oils, together with hydrocarbons such as alkylated naphthalene,tetrahydronaphthalene, xylene mixtures, cyclohexanols, and optionally inaddition ketones, chlorinated hydrocarbons such as tetrachloroethane,trichloroethylene, or triand tetrachlorobenzenes.

For use in aqueous application forms, emulsion concentrates, pastes orwettable spraying powders are used with the addition of water. Asemulsifiers or dispersants there can be used non-ionogenic products, e.g. condensation products of aliphatic alcohols, amines or carboxylicacids with a long chain hydrocarbon residue of from 10 to 30 carbonatoms with ethylene oxide, for example the condensation product ofoctadecyl alcohol and 25 to 30 mols ethyleneoxide, or that of soya fattyacid and 30 mols ethylene oxide or that of technical oleylamine and 15mols ethyleneoxide or that of dodecylmercaptan and 12 molsethyleneoxide. I-Iowever condensation products of ethyleneoxide withhydroaromatic-polycyclic carboxylic acids and amines can also be used.Amongst anionic emulsifying agents which may be used there should bementioned: the sodium salt of dodecylalcoholsulphonate esters, thesodium salt of dodecylbenzenesulfonic acid, the potassium ortriethanolamine salt of oleic acid or of abietic acid or of mixtures ofthese acids, or the sodium salt of a petroleum sulphonic acid. Ascationic dispersing agents, there can be used quaternary ammonium andphosphonium compounds, e.g. cetylpyridiniumchloride ordioxyethylbenzyldodecylammonium chloride. If the active substance of theinvention is to be used in the form of a dusting or scatteringpreparation, then it can contain talcum, kaolin, bentonite, sand,calcium car bonate, calcium phosphate or even coal as solid carriermaterials. Evaporating agents can also be added to the stored goods suchas, for example, porous clay bars impregnated with the active agent. Thevarious preparations can contain in customary fashion the addition ofmaterials which improve the distribution, the adhesive strength, or thepenetration depth; among such materials should be mentioned fatty acids,resins, glues, casein, or e.g. alginates. The use of preparations ingranulated form is also very useful. The compound of the invention canbe present as sole active material in the pest control agents, or it maybe in combination with other insecticides or acaricides.

The following Examples will serve to illustrate the invention:

EXAMPLE 1 27.6 parts of the sodium salt of a-hydroxymethylenepropionicacid methyl-ester,

were warmed in 200 parts by volume of acetonitrile to 40-50C. At thistemperature, 33 parts of dimethylthiochlorophosphate were added dropwiseand the mixture then maintained for 4 hours with stirring at 40-50C.After cooling, the salts were filtered off with suction and the solventremoved in vacuo at 50C bath temperature. The residue was taken up inmethylene chloride and rinsed with N caustic soda. After the evaporationof the solvent in vacuo, the active substance according to the inventionof the formula was obtained in the form of an oil.

The compound boiled at 80-90C (0.01 mm Hg).

EXAMPLE 2 A. Dusting agent Equal parts of the active agent according tothe invention and precipitated silica were finely ground. By mixing withkaolin or talcum, it was possible to manufacture dusting agents with thepreferred l6% content 5 of active substance.

B. Powder for spraying For the manufacture of a water soluble sprayingpowder, the following components were mixed and finely ground:

50 parts active agent of formula I 20 parts highly absorbent silica 25parts Bolus alba (Kaolin) 1.5 parts sodiuml-benzyl-2-stearyl-benzimidazol- 6,3-disulphonate.

3.5 parts of a reaction product of p-tert. octylphenol andethyleneoxide.

C. Emulsion concentrates a. 40 parts of the active substance of formulaI were mixed with 10 parts of a mixture of 'an anionic surface activecompound, preferably the calcium or magnesium salt ofmonolaurylbenzenemonosulphonic acid, and a nonionic surface activecompound, preferably a polyethyleneglycolether'of monosorbitollaureate,and

the whole dissolved in a little xylene. The solution was then made upwith xylene to 100 ml and a clear solution was thus obtained which couldbe used as a spraying agent concentrate and which gave a stable emulsionon being poured into water;

b. it was also possible to formulate an emulsion concentrate accordingto the following instruction:

20 parts active agent parts xylene 10 parts of a mixture of a reactionproduct of an alkylphenol with ethyleneoxide andcalciumdodecylbenzenesulphonate were mixed together. On dilution withwater to the desired concentration, a spayable emulsion resulted.

D. Granulate 7.5 grams of the active agent of the formula were dissolved in ml acetone and the so obtained acetonic solution added to 92grams of coarsely granulated attapulgite.

The whole was well mixed and the solvent was removed in a rotaryevaporator. A granulate was obtained with 7.5% active substance content.

EXAMPLE 3 Gas Action against adult houseflies Mortality time for a Acuteoral toxicity LD percentage of the houseflies (mg/kg) Active substance10% 50% 100% (rats) Phosdrin (Registered v Trade Mark) 22' 25 30' 3-7Compound I 5' 8' 25' 500 EXAMPLE 4 Ingestion test with one day oldhouseflies (Musca domestica) Dilution series were manufactured withwater. As solvent for the test preparations and similarly as a nutritionagent for the flies, 30% sugar water was used which had been colouredwith chlorantin light red (as an attractant). The dilutions were testedwith one day old houseflies. The l, 2 and 4 hour controls enabled thespeed of action to be determined. By means of the 24 hour control thelimit concentration (action strength) could also be determined.

EXAMPLE 6 Diffusion action in wheat flies killed with active agentActive substance Concentration Phosdrin in 30% sugar water afterall-exposure time (hours) Compound 1 PP'" l 2 4 24 I00 lOO -lOO I00 100I00 lOO I00 I00 50 30 70 80 I00 60 99 I00 I00 25 20 40 60 100 40 70 100I00 12 0 0 20 90 40 70 I00 I00 6 O 0 I0 80 I00 100 3 O O O 20 IO 20 5O90 1.5 0 0 O 0 0 0 0 l0 0.8 0 0 0 0 0 0 0 0 0.4 0 0 0 0 0 0 0 0 EXAMPLE5 D bili test between DDVP d C d 1 3O ggfszion of active substance ingas phase between the wheat Method Wheat was shaken up with 5% dustingagent and then (Test Animal Sit. Granarius) Distance in cm from theMortality in after 7 days treated wheat layer exposure time with mixedagain repeatedly with untreated wheat at half the DDVP Compound I poisonconcentration. In this way, a dilution series with 1 100 muconcentrations of 50 25 12 6 3 1.5 ppm 1 100 00 was obtained. In orderto allow the duration differences 2 8 :88 between DDVP and Compound 1 tobe demonstrated 5 0 90 even better, the containers filled with thetreated wheat 6 O (sized for 500 grams of wheat) were stored unsealed.40

Since the test is repeated once per month, the desired information isobtained concerning the residual effect. We clam: In the test, theimportant pests in storage protection The compound of formula werechosen, viz. the grain weevil (Sitophilus granarius) lesser grain borer(Rhizopertha dominica) 5 u and the larvae of the Khapra beetle(Trogoderma (CH:O)2P O CH COOCHS granarium), which are very resistant toinsecticides. 20 test insects were tested per concentration and the results are expressed in the following table.

Table l Disinfection test with DDVP and Compound I on Wheat DDVP(Dimethyldichlorvinylphosphate) 20 test animals per concentrationanimals dead after one week exposure, at

Treated Silophilus granuriu: Rh izopertlm dominion Trogoderma granarium(L) Wheat concentration of active substance in wheat (ppm) Stored For 25I2 6 3 1.5 50 25 25 12 6 3 1.5

fresh 100 I00 I00 I00 I00 100 I00 I00 I00 I00 100 95 100 I00 100 100 10085 1 month 100 100 I00 25 5 0 I00 l5 l0 5 0 I00 5 0 O O 2 months 100 I0055 0 0 0 95 40 2O 5 0 5 45 I0 0 O 0 0 3 months 95 50 0 0 0 0 15 0 0 O 00 0 O 0 0 0 Compound fresh I00 I00 I00 100 I00 I00 I00 100 I00 I00 20100 I00 I00 I00 90 l month I00 I00 I00 I00 90 I00 I00 85 60 5 O 100 I0095 85 I0 0 2 months 100 I00 I00 I00 I00 I00 I00 80 70 40 l0 I5 I00 I0085 30 0 0 3 months 100 I00 100 I00 i 95 70 I00 75 35 l5 15 0 I00 I00 55l0 0 0 Control fresh 0 O O l month 0 0 0 2 months 0 5 O 3 months 0 0 O

1. THE COMPOUND OF FORMULA